Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/90—Block copolymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q3/00—Manicure or pedicure preparations
  • A61Q3/02—Nail coatings
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • A61K8/8105—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • A61K8/8117—Homopolymers or copolymers of aromatic olefines, e.g. polystyrene; Compositions of derivatives of such polymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/54—Polymers characterized by specific structures/properties

Definitions

• the present invention relates to new cosmetic or dermatological compositions topical, comprising particular copolymers, in particular amphiphilic gradient copolymers, preferably soluble or dispersible in water and / or in organic solvents.
• compositions making it possible to obtain a deposit, in particular adhesive or film-forming, on the keratin materials considered, such as the hair, the skin, the eyelashes or the nails.
• these compositions can provide color (makeup or hair coloring compositions), shine or mattness (skin care or makeup compositions), physical properties such as shaping ( hair compositions, especially styling compositions), care or protective properties (care compositions, for example of hydration or UV protection).
• good persistence and resistance over time of the cosmetic deposit are sought, as well as good adhesion to the support.
• this deposit be able to resist mechanical attack such as friction, transfers by contact with another object; with water, sweat, tears, rain, sebum and oils.
• the object of the present invention is to overcome the drawbacks of the prior art by proposing a cosmetic or dermatological composition comprising specific polymers, which avoid demixing problems within the formula while providing the desired cosmetic properties.
• An object of the present invention is a cosmetic or dermatological composition
• a cosmetic or dermatological composition comprising at least one gradient copolymer comprising at least two different monomers, and having a mass polydispersity index (Ip) less than or equal to 2.5 preferably between 1.1 and 2.3, in particular between 1.15 and 2.0, or even between 1.2 and 1.9 or 1.8.
• the gradient copolymers according to the invention have a low dispersity in composition, all the chains having almost the same structures, they are therefore compatible with each other; it follows that the cosmetic compositions comprising these copolymers do not have the drawbacks and limitations of the compositions of the prior art.
• the copolymers according to the invention have the advantage of being easy to handle in water or in an organic solvent medium, while retaining advantageous rheological properties.
• the copolymers according to the invention are gradient copolymers, which comprise at least two different monomers, and which have a polydispersity in low mass and preferably a polydispersity in low composition.
• Mass polydispersity can be illustrated using the mass polydispersity index (Ip) of the copolymer, which is equal to the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) .
• Ip mass polydispersity index
• Mw weight average molecular weight
• Mn number average molecular weight
• a low mass dispersity translates approximately identical chain lengths, which is the case for the copolymers according to the present invention.
• the gradient copolymer according to the invention has a mass polydispersity index less than or equal to 2.5, preferably between 1.1 and 2.3, in particular between 1.15 and 2.0, or even between 1.2 and 1.9 or 1.8.
• the weight-average molecular weight of the gradient copolymer is preferably between 5000 g / mol and 1,000,000 g / mol, in particular between 5,500 g / mol and 800,000 g / mol, and even better between 6000 g / mol and 500,000 g / mol.
• the number-average molecular weight of the gradient copolymer is between 5,000 g / mol and 1,000,000 g / mol, in particular between 5,500 g / mol and 800,000 g / mol, and even better still between 6,000 g / mol and 500,000 g / mol.
• the average molecular weights in weight (Mw) and in number (Mn) are determined by gel permeation liquid chromatography (GPC), eluent THF, calibration curve established with linear polystyrene standards, refractometric detector).
• the gradient copolymer according to the invention also preferably has low dispersity in composition. This means that all channels of copolymers have a composition (that is to say a chain of monomers) approximately analogous and are therefore homogeneous in composition.
• LAC liquid adsorption chromatography
• LAC adsorption chromatography curve
• the dispersity in composition can also be defined by the value of w as defined above.
• said value w is between 1 and 3, in particular between 1.1 and 2.3 and even better between 1.1 and 2.0.
• the polymer chains of the gradient copolymers according to the invention grow simultaneously and therefore incorporate at all times the same ratio of co-monomers. All chains therefore have the same or similar structures, resulting in a low dispersity in composition. These chains also have a low mass polydispersity index.
• Gradient copolymers are copolymers exhibiting an evolution of the ratio of the various monomers throughout the chain. The distribution in the polymer chains of the comonomers depends on the evolution during the synthesis of the relative concentrations of the comonomers.
• the copolymers according to the invention comprise at least two different monomers whose concentration along the polymer chain changes gradually and systematically and predictably.
• a random polymer obtained by conventional radical polymerization of two monomers is distinguished from a gradient copolymer, by the distribution of the monomers which is not identical on all the chains, and by the length of said chains. channels which is not identical for all channels.
• a natural gradient copolymer is a gradient copolymer synthesized in batch from an initial mixture of the co-monomers. The distribution in the chain of the various monomers follows a law deduced from the relative reactivity and the initial concentrations of monomers. These copolymers are the simplest class of gradient copolymers because it is the initial blend that defines the final product property.
• An artificial gradient copolymer is a copolymer whose variation is concentration of monomers during synthesis by a process device. In this case, we pass from a mixture of monomers to another in the chain due to a sudden and sudden change of the monomers in the reaction medium (stripping of the first mixture or addition of at least one new monomer). There may even be a clear disappearance of one or more of the monomers for the benefit of one or more others.
• the experimental characterization of the gradient is provided by the measurement during polymerization of the chemical composition of the polymer. This measurement is made indirectly by determining the evolution of the content of the various monomers at all times. It can be done by NMR and UV, for example. Indeed, for polymers prepared by living or pseudo-living polymerization, the length of the chains is linearly linked to the conversion. By taking a sample of the polymerization solution, at different times of the polymerization and by measuring the difference in content of each monomer, this gives access to the composition of the gradient.
• the distribution of chain compositions is narrow. In particular, there is no overlap between the peak of the copolymer gradient and those of the respective homopolymers. This means that the material obtained in gradient consists of polymer chains of the same composition whereas in conventional statistical polymerization, different kinds of chain coexist, including those of the respective homopolymers.
• the factors determining the gradient are on the one hand the relative reactivity coefficients of each monomer (called r i for the monomer Mi) which depend mainly on the type of synthesis process used (homogeneous, dispersed) and the solvents, and on the other hand apart from the initial concentrations of each of the monomers, as well as any additions of monomers during the polymerization.
• r i the relative reactivity coefficients of each monomer
• M1 styrene gradient
• M2 methacrylic acid
• the variation of the initial styrene and methacrylic acid concentrations makes it possible to obtain different gradient copolymers having chains of completely different structures.
• the initial methacrylic acid concentration is 10% by weight, a very low gradient copolymer is obtained in the end, from which nanostructuring cannot be expected.
• this initial concentration is 20% by weight, a gradient copolymer is obtained having a hydrophilic "head” and a hydrophobic "tail” with a gradient sufficiently pronounced to lead to nanostructuring.
• this concentration is 50% by weight, the monomers being isoreactive under these conditions, the copolymer obtained is of the alternating type.
• copolymers described are all copolymers with a gradient of styrene and methacrylic acid, the difference in initial concentration of the monomers leads to chains of completely different structures giving the copolymers different properties. This example therefore illustrates the importance of the initial monomer compositions on the arrangement along the chain of the different monomers.
• the structure of these polymers can be determined by the disappearance of the acid methacrylic depending on the conversion rate.
• the gradient copolymer according to the invention comprises at least two monomers different, which can each be present in an amount of 1 to 99% by weight relative to the final copolymer, in particular at a rate of 2-98% by weight, of preferably at a rate of 5-95% by weight.
• the gradient copolymer comprises at least one hydrophilic monomer, or a mixture of hydrophilic monomers.
• hydrophilic monomers can be present in an amount of 1 to 99% by weight, in particular 2-70% by weight, better still 5-50% by weight, or even 10-30% by weight, relative to the total weight of the copolymer.
• hydrophilic monomer will denote either the monomers whose homopolymers are soluble or dispersible in water, or whose ionic form is.
• a homopolymer is said to be water-soluble if it forms a clear solution when it is in solution at 1% by weight in water, at 25 ° C.
• a homopolymer is said to be water-dispersible if, at 1% by weight in water, at 25 ° C, it forms a stable suspension of fine particles, generally spherical.
• the average size of the particles constituting said dispersion is less than 1 ⁇ m and, more generally, varies between 5 and 400 nm, preferably from 10 to 250 nm. These particle sizes are measured by light scattering.
• the hydrophilic monomer at a Tg greater than or equal to 20 ° C., in particular greater than or equal to 50 ° C., but may possibly have a Tg less than or equal to 20 ° C.
• the gradient copolymer can also comprise at least one monomer hydrophobic, in particular of hydrophobic monomer capable of being rendered hydrophilic after polymerization, or a mixture of such monomers.
• the monomer (s) hydrophobic can be made hydrophilic (s) for example by reaction chemical in particular by hydrolysis, or by chemical modification, in particular of an ester function by incorporating chains with a pattern hydrophilic, for example of the carboxylic acid type.
• hydrophobic monomers can be present in an amount of 1 to 99% by weight, in particular 30-98% by weight, better still 50-95% by weight, or even 70-90% by weight, relative to the total weight of the copolymer.
• the hydrophobic monomers capable of being made hydrophilic may be present in an amount of 1 to 99% by weight, in particular 5-50% by weight, and better still 8-25% by weight, relative to the total weight of the copolymer.
• the hydrophobic monomer at a Tg greater than or equal to 20 ° C., in particular greater than or equal to 30 ° C., but may optionally have a Tg less than or equal to 20 ° C.
• the gradient copolymer according to the invention comprises at least one monomer having a Tg less than or equal to 20 ° C, in particular between -150 ° C and 20 ° C, more particularly between -130 ° C and 18 ° C, and even better between -120 ° C and 15 ° C, or a mixture of such monomers.
• These monomers of Tg ⁇ 20 ° C can be present in an amount of 1 to 99% by weight, in particular 10-90% by weight, even better 20-80% by weight, or even 50-75% by weight, relative to the weight total of the copolymer.
• the monomers of Tg ⁇ 20 ° C can therefore be present in an amount of 1 to 99% by weight, especially 10-90% by weight, even better 20-80% by weight, even 25-50% by weight, relative to the total weight of the copolymer.
• Tg monomer will denote the monomers whose homopolymer has such a Tg, measured according to the method described below.
• the Tg (or glass transition temperature) is measured according to ASTM D3418-97, by differential enthalpy analysis (DSC "Differential Scanning Calorimetry) on a calorimeter, over a temperature range between -100 ° C and + 150 ° C at a heating rate of 10 ° C / min in 150 ⁇ l aluminum crucibles.
• DSC differential enthalpy analysis
• the gradient copolymer according to the invention comprises three different monomers, which may be present in an amount of 5-90% by weight each, in particular 7-86% by weight each relative to the total weight of the copolymer .
• the copolymer can comprise 5-25% by weight of a first monomer, 5-25% by weight of a second monomer and 50-90% by weight of a third monomer.
• the copolymer according to the invention can comprise 5-25% by weight of a hydrophilic monomer, 50-90% by weight of a Tg monomer less than or equal to 20 ° C and 5-25% by weight of an additional monomer.
• the hydrophilic monomers are chosen from methacrylate N, N-dimethylaminoethyl (MADAME), acrylic acid, methacrylic acid, crotonic acid, styrenesulfonic acid, acrylamidopropanesulfonic acid, dimethylaminopropylmethacrylamide (DMAPMA); styrene sulfonate, hydroxyethyl acrylate, glycerol acrylate, methacrylate ethoxyethyl, ethoxyethyl acrylate, methoxypolyethylene (meth) acrylate glycol (8 or 12OE); hydroxypolyethylene glycol (meth) acrylate; N-vinylpyrrolidone, N-vinylcaprolactam, acrylamide, N, N-dimethylacrylamide.
• MADAME N-dimethylaminoethyl
• DMAPMA dimethylaminopropylmethacrylamide
• hydrophobic monomers capable of being made hydrophilic in particular by hydrolysis, mention may be made of C1-C4 alkyl (meth) acrylates, such as tert-butyl (meth) acrylate or ethyl (meth) acrylate, which lead to obtaining (meth) acrylic acid after hydrolysis.
• C1-C4 alkyl (meth) acrylates such as tert-butyl (meth) acrylate or ethyl (meth) acrylate, which lead to obtaining (meth) acrylic acid after hydrolysis.
• a difunctional initiator and a mixture of monomers will preferably be chosen such that the reactivity of the hydrophilic monomers is greater than that of the other monomers.
• the radical polymerization initiator can be chosen from all the initiators usual polymerizations, such as azo compounds and in particular azobisisobutyronitrile, or of peroxide type such as peroxides organic with 6-30 carbon atoms, including benzoyl peroxide.
• a nitroxide / initiator molar ratio of between 1 is respected. and 2.5; this ratio can be between 2 and 2.5 when considering that a mole of initiator gives rise to two moles of polymer chains, and can be between 1 and 1.25 for monofunctional initiators.
• alkoxyamine of formula (II) a nitroxide of formula (I), in a proportion ranging from 0 to 20 mol% relative to the moles alkoxyamine functions (one mole of multivalent alkoxyamine provides a number of alkoxyamine functions proportional to its valence), so that improve the quality of the polymerization control.
• the gradient copolymers according to the invention can be present in the topical cosmetic or dermatological compositions in an amount of 0.1 to 60% by weight, preferably 0.5 to 40% by weight, especially 1 to 35% by weight, even 5-30% by weight, relative to the total weight of the composition.
• copolymers can be present in the composition in dissolved form, for example in water or an organic solvent, or in the form of aqueous or organic dispersion.
• an aqueous solution of the copolymer directly by mixing the polymer with water, optionally by heating. It is also possible to dissolve the polymer in an organic solvent with a boiling point lower than water (for example acetone or methyl ethyl ketone), at a solid content of between 20 and 90% by weight.
• a solution preferably at least 1 M base such as a hydroxonium ion salt (OH - ), an amine (ammonia), a carbonate (CO 3 2- ) or hydrogen carbonate (HCO 3 - ) or organic neutralizing salt.
• a solution preferably at least 1M, of acid can be added. Water is then added to the solution with vigorous stirring in a proportion such that the solid content obtained is between 1 and 80% by weight.
• the water can be replaced by a hydroalcoholic mixture, in proportions ranging from 99/1 to 50/50.
• the solvent is evaporated by stirring the solution at 100 ° C. Concentration continues until the desired solid level is obtained.
• the gradient copolymers according to the invention are very particularly soluble or dispersible in water and / or in organic solvents, in particular C1-C6 monoalcohols, such as ethanol or isopropanol, or esters of carboxylic acids having a total of 3 to 10 carbon atoms, such as butyl acetate, and that they can be dissolved in large quantities without affecting the viscosity of the solution.
• C1-C6 monoalcohols such as ethanol or isopropanol
• esters of carboxylic acids having a total of 3 to 10 carbon atoms such as butyl acetate
• the gradient polymers according to the invention lead to a lower viscosity, in comparison with the usual diblock copolymers; these copolymers can therefore be introduced into a formulation without significantly modifying the viscosity.
• these polymers have a low viscosity even at a concentration of up to 20% by weight of copolymer in water.
• an aqueous solution at 20% by weight of said copolymers could advantageously have a viscosity of between 1 and 10,000 centipoises, in particular 1 and 5000 cp, and even better 5 and 1000 cp, at 25 ° C ( viscosity measured with a Brookfield viscometer, needle module (spindle), the module being chosen according to the viscosity of the solution).
• compositions according to the invention comprise, in addition to said copolymers, a physiologically acceptable medium, in particular cosmetically or dermatologically acceptable, i.e. a medium compatible with keratin materials such as facial skin or body, hair, eyelashes, eyebrows and nails.
• a physiologically acceptable medium in particular cosmetically or dermatologically acceptable, i.e. a medium compatible with keratin materials such as facial skin or body, hair, eyelashes, eyebrows and nails.
• the composition can thus comprise, a hydrophilic medium comprising water or a mixture of water and organic solvent (s) hydrophilic (s) such as alcohols and in particular linear or branched lower monoalcohols having from 2 to 5 carbon atoms such as ethanol, isopropanol or n-propanol, and polyols such as glycerin, diglycerin, propylene glycol, sorbitol, pentylene glycol, and polyethylene glycols, or even C ethers 2 and hydrophilic C 2 -C 4 aldehydes.
• the water or the mixture of water and hydrophilic organic solvents may be present in the composition according to the invention in a content ranging from 0.1% to 99% by weight, relative to the total weight of the composition, and preferably 10% to 80% by weight.
• the composition may also comprise a fatty phase, in particular consisting of fatty substances liquid at room temperature (25 ° C. in general) and / or fatty substances solid at ambient temperature such as waxes, pasty fatty substances, gums and their mixtures. .
• fatty substances can be of animal, vegetable, mineral or synthetic origin.
• This fatty phase can, in addition, contain lipophilic organic solvents.
• oils As fatty substances liquid at room temperature, often called oils, which can be used in the invention, mention may be made of: hydrocarbon oils of animal origin such as perhydrosqualene; vegetable hydrocarbon oils such as liquid triglycerides of fatty acids with 4 to 10 carbon atoms such as heptanoic or octanoic acid triglycerides, or even sunflower, corn, soybean, grape seed, sesame oils, apricot, macadamia, castor, avocado, caprylic / capric acid triglycerides, jojoba oil, shea butter; linear or branched hydrocarbons, of mineral or synthetic origin such as paraffin oils and their derivatives, petrolatum, polydecenes, hydrogenated polyisobutene such as parlameam; synthetic esters and ethers, in particular of fatty acids such as, for example, Purcellin oil, isopropyl myristate, ethyl-2-hexyl palmitate, octyl-2
• composition according to the invention can also comprise one or more organic solvents, cosmetically acceptable (tolerance, toxicology and touch acceptable). These solvents can generally be present in a content ranging from 0 to 90%, preferably from 0.1 to 90%, more preferably from 10 to 90% by weight, relative to the total weight of the composition, and better still from 30 90%.
• solvents which can be used in the composition of the invention there may be mentioned, in addition to the hydrophilic organic solvents mentioned above, ketones which are liquid at room temperature such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, isophorone, cyclohexanone, acetone; propylene glycol ethers which are liquid at room temperature such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol mono n-butyl ether; short chain esters (having 3 to 8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate, acetate d 'isopentyle; ethers liquid at room temperature such as diethyl ether, dimethyl ether or dichlorodiethyl ether; alkanes which are liquid at room temperature such as decan
• wax within the meaning of the present invention is meant a lipophilic compound, solid at room temperature (25 ° C), with reversible solid / liquid state change, having a melting point greater than or equal to 30 ° C up to 'at 120 ° C.
• melting By bringing the wax to the liquid state (melting), it is possible to make it miscible with the oils which may be present and to form a homogeneous mixture microscopically, but by bringing the temperature of the mixture to room temperature, one recrystallizes the wax in the oils of the mixture.
• the melting point of the wax can be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name DSC 30 by the company METLER.
• DSC differential scanning calorimeter
• the waxes can be hydrocarbon, fluorinated and / or silicone and be of vegetable, mineral, animal and / or synthetic origin.
• the waxes have a melting temperature above 25 ° C and better still above 45 ° C.
• the gums are generally high molecular weight polydimethylsiloxanes (PDMS) or cellulose gums or polysaccharides and the pasty bodies are generally hydrocarbon compounds such as lanolines and their derivatives or PDMS.
• PDMS polydimethylsiloxanes
• the nature and quantity of the solid bodies are a function of the mechanical properties and of the desired textures.
• the composition may contain from 0 to 50% by weight of waxes, relative to the total weight of the composition and better still from 1 to 30% by weight.
• the composition according to the invention may also comprise one or more coloring matters chosen from water-soluble dyes, liposoluble dyes, and pulverulent dyestuffs such as pigments, pearlescent agents and flakes well known to those skilled in the art.
• the coloring matters may be present in the composition in a content ranging from 0.01 to 50% by weight, relative to the weight of the composition, preferably from 0.01 to 30% by weight.
• the term “pigments” should be understood to mean particles of any shape, white or colored, mineral or organic, insoluble in the physiological medium, intended to color the composition. By nacres, it is necessary to understand particles of any iridescent shape, in particular produced by certain molluscs in their shell or else synthesized.
• the pigments can be white or colored, mineral and / or organic.
• mineral pigments mention may be made of titanium dioxide, optionally surface-treated, zirconium or cerium oxides, as well as oxides of zinc, iron (black, yellow or red) or chromium, violet of manganese, ultramarine blue, chromium hydrate and ferric blue, metallic powders such as aluminum powder, copper powder.
• organic pigments mention may be made of carbon black, pigments of D & C type, and lakes based on cochineal carmine, barium, strontium, calcium, aluminum.
• the pearlescent pigments can be chosen from white pearlescent pigments such as mica coated with titanium or bismuth oxychloride, colored pearlescent pigments such as titanium mica coated with iron oxides, mica titanium coated with in particular blue ferric or chromium oxide, titanium mica coated with an organic pigment of the aforementioned type as well as pearlescent pigments based on bismuth oxychloride.
• water-soluble dyes mention may be made of the disodium salt of culvert, disodium salt of alizarin green, quinoline yellow, trisodium salt amaranth, disodium salt of tartrazine, monosodium salt of rhodamine, disodium salt of fuchsin, xanthophyll, methylene blue.
• the composition according to the invention can furthermore comprise one or more fillers, in particular in a content ranging from 0.01% to 50% by weight, per relative to the total weight of the composition, preferably ranging from 0.01% to 30% in weight.
• fillers By charges, it is necessary to include particles of any shape, colorless or white, mineral or synthetic, insoluble in the medium of composition regardless of the temperature at which the composition is made. These charges are used in particular to modify the rheology or the texture of the composition.
• the fillers can be mineral or organic of any shape, platelet-shaped, spherical or oblong, whatever the crystallographic shape (for example sheet, cubic, hexagonal, orthorhombic, etc.).
• the composition may also comprise an additional polymer such as a film-forming polymer.
• a film-forming polymer a polymer capable of forming on its own or in the presence of an agent film-forming aid, a continuous and adherent film on a support, in particular on keratin materials.
• film-forming polymers susceptible to be used in the composition of the present invention mention may be made of synthetic polymers, of radical type or of polycondensate type, the polymers of natural origin and mixtures thereof, in particular polymers acrylics, polyurethanes, polyesters, polyamides, polyureas, cellulosic polymers such as nitrocellulose.
• composition according to the invention can also comprise ingredients commonly used in cosmetics, such as vitamins, thickeners, gelling agents, trace elements, softeners, sequestrants, perfumes, alkalizing or acidifying agents, preservatives, sun filters, surfactants, antioxidants, hair loss agents, anti-dandruff agents, propellants, ceramides, or mixtures thereof.
• ingredients commonly used in cosmetics such as vitamins, thickeners, gelling agents, trace elements, softeners, sequestrants, perfumes, alkalizing or acidifying agents, preservatives, sun filters, surfactants, antioxidants, hair loss agents, anti-dandruff agents, propellants, ceramides, or mixtures thereof.
• ingredients commonly used in cosmetics such as vitamins, thickeners, gelling agents, trace elements, softeners, sequestrants, perfumes, alkalizing or acidifying agents, preservatives, sun filters, surfactants, antioxidants, hair loss agents, anti-dandruff agents, propellants, ceramides,
• the composition according to the invention can be in particular in the form of a suspension, dispersion, solution, gel, emulsion, in particular oil-in-water (O / W) or water-in-oil (W / O) emulsion ), or multiple (W / O / W or polyol / O / W or O / W / O), in the form of a cream, paste, foam, vesicle dispersion, in particular of ionic lipids or not, of biphase lotion or multiphase, spray, powder, paste, especially flexible paste (especially paste having dynamic viscosity at 25 ° C of the order of 0.1 to 40 Pa.s under a shear speed of 200 s -1 , after 10 minutes of measurement in cone / plane geometry).
• the composition can be anhydrous, for example it can be an anhydrous paste.
• the composition according to the invention may be a makeup composition, in particular a product for the complexion such as a foundation, a blush or an eyeshadow; a lip product such as lipstick or lip care; a concealer; a blush, a mascara, an eyeliner; an eyebrow makeup product, a lip or eye pencil; a nail product such as nail polish or nail care; a body makeup product; a hair makeup product (mascara or hair spray).
• the composition according to the invention may be a composition for protecting or caring for the skin of the face, the neck, the hands or the body, in particular an anti-wrinkle, anti-fatigue composition making it possible to give a radiant boost to skin, a moisturizing or treating composition; an anti-sun or artificial tanning composition.
• the composition according to the invention can also be a hair product, in particular for maintaining the hairstyle or shaping the hair.
• the hair compositions are preferably shampoos, gels, styling lotions, brushing lotions, fixing compositions and styling such as hairsprays or spray.
• Lotions can be packaged in various forms, in particular in vaporizers, pump dispensers or in aerosol containers to ensure application of the composition in vaporized form or in foam form. Such forms packaging are indicated, for example when it is desired to obtain a spray, a foam for fixing or treating hair.
• the invention also relates to a cosmetic make-up or care process.
• keratin materials in particular the skin of the body or of the face, nails, hair and / or eyelashes, comprising application to said materials a cosmetic composition as defined above.
• the polymerization initiators mentioned in the examples are alkoxyamines called 'DIAMS' and 'MONAMS' which correspond to the following formulas:
• the trace of the polymer shows the low polydispersity of the chemical composition of the chains.
• the dispersity in composition (or w) is 1.6.
• a schematic representation of the copolymer obtained can be as follows: in which the dark spheres denote the styrene / methacrylic acid sequences, and the white spheres denote the ethyl acrylate sequences.
• LAC adsorption chromatography liquid
• aqueous dispersion at 10% solid content is prepared of the copolymer prepared in Example 2a. To do this, the polymer is previously dried in an oven. Then, 10 g of polymer are dissolved in 90 ml of water comprising 1.6 g of AMP (amino-2-methyl-2-propanol). A clear and very fluid aqueous dispersion is obtained. The particle size, measured by diffusion (Coulter 4NW device) is 33 nm.
• An aqueous dispersion of the copolymer prepared in Example 1 is prepared. 10 g of polymer are dissolved in 40 g of tetrahydrofuran; 1.41 g of AMP (amino-2-methyl-2-propanol) dissolved in 10 ml of water are added. The solution thickens. 90 ml of demineralized water are then added slowly and with vigorous stirring. The solution remains clear and becomes fluid again. The solvent is evaporated and a clear and fluid aqueous dispersion is obtained. The particle size, measured by diffusion (Coulter 4NW device) is 199 nm.
• the polymers of Examples 1 and 2a are dissolved in butyl acetate, so as to obtain a solution having a dry matter content of 20% by weight (viscosity at 25 ° C: less than 500 cp). A composition is obtained which can be applied to the nail. It is also possible to pigment it.
• the rheological properties of an aqueous gel at 22.3% by weight of poly (butyl acrylate) / (styrene / neutralized methacrylic acid) copolymer according to the invention are studied, in comparison with those of aqueous gels at different concentrations. of poly (butyl acrylate) / (styrene / neutralized methacrylic acid) diblock copolymer.
• the measurements were carried out at 25 ° C. using an imposed constraint rheometer, Haake RS150, equipped with a sandblasted titanium measuring body fitted with a anti-evaporation device.
• a plane-cone measuring body was used with a diameter 6 cm and 2 ° angle. The sample was carefully placed (speed 0.6 mm / min) and a rest time of 2 minutes was observed before the start of the measurements.
• the copolymer according to the invention is characterized by a low consistency, especially at low frequency, which increases with the stress. It also has a pronounced liquid character almost unchanged throughout the frequency domain studied (0.01, 1 and 10 Hz).
• the comparison of linear viscoelastic properties obtained at a frequency of 1 Hz for the gradient copolymer and the diblock copolymer highlights evidence of differences in properties and behaviors between the two copolymers.
• the 22.3% gradient copolymer has a fairly consistent low which lies between those of the diblock copolymer gels, at concentrations 2.4 and 1.04%.
• the gradient copolymer differs from the copolymer diblock by its pronounced liquid nature which is not obtained even for lower concentrations of diblock copolymer.
• the gradient copolymer according to the invention is characterized by a low consistency and a pronounced liquid character, while the chemically equivalent diblock copolymer is characterized by a high consistency and a pronounced solid character, even for much lower concentrations ( up to 2%).
• the gradient copolymer has a relatively low viscosity at rest (up to 20 times lower) than that of the diblock copolymer; it fluidizes little and slowly under the effect of shearing, compared to the diblock copolymer.
• a system obtained with a gradient copolymer, used even at high concentration is less thickened (low viscosity at rest) than that obtained with a chemically equivalent diblock, used at a significantly lower concentration.

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